Aqueous composition that can be hardened physically, thermally or thermally and with actinic radiation and the derivatives and production thereof

ABSTRACT

The invention concerns a novel aqueous composition that can be hardened physically, thermally and/or with actinic radiation, containing a compound of general formula (I): X[NH—C(═O)—NH—Y—NH—C(═O)—OR]2 having at least one urea and urethane group, wherein the variables have the following meaning: R represents identical or different polyalkylene glycol ether radicals; X represents a bivalent substituted or unsubstituted arylene radical; Y represents identical bivalent substituted or unsubstituted arylene radicals, which are the same as or different from radical X or different bivalent substituted or unsubstituted arylene radicals of which none or one is identical to radical X. The invention also concerns the utilization of said compound for the production of novel aqueous coating materials, adhesives and sealants that can be hardened physically, thermally or thermally and with actinic radiation and their derivatives.

[0001] The present invention relates to novel aqueous compositionscurable physically, thermally, or thermally and with actinic radiation,and comprising Theological aids based on urea urethanes. The presentinvention also relates to the use of the novel compositions to preparenovel aqueous coating materials, adhesives, and sealing compounds. Thepresent invention additionally relates to novel processes for preparingnovel aqueous coating materials, adhesives, and sealing compounds fromaqueous or aqueous/organic compositions curable physically, thermally,or thermally and with actinic radiation and comprising rheological aidsbased on urea urethanes. The present invention further relates to novelcoatings, adhesive films, and seals which are produced with the aid ofthe novel coating materials, adhesives, and sealing compounds and/or ofthe novel processes.

[0002] Thermally curable aqueous coating materials which comprise acrosslinking agent and an ionically and/or nonionically stabilizedpolyurethane which is saturated, unsaturated, and/or grafted witholefinically unsaturated compounds and is based on aliphatic,cycloaliphatic, aliphatic-cycloaliphatic, aromatic, aliphatic-aromaticand/or cycloaliphatic-aromatic polyisocyanates, and also thecorresponding coatings, are known, for example, from the patents EP-A-0089 497, DE-C-197 22 862, and DE-A-196 45 761. They are normallyreferred to as aqueous basecoat materials. The special rheologicalproperties required for the storage and application of these knownaqueous basecoat materials, such as viscosity, pseudoplasticity andthixotropy, are formulated through the use of an inorganicphyllosilicate of the montmorillonite type. Its use is necessary inorder to give the aqueous basecoat material its familiarly goodperformance properties such as, for example, good atomizability,stability, and, in the case of effect aqueous basecoat materials, anexcellent metallic effect, i.e., a very highly pronounced flip-flopeffect. Furthermore, in preparing the known aqueous basecoat materialsit is necessary to insert a homogenization step following the additionof each constituent, so making production comparatively complex.

[0003] Unfortunately, the inorganic phyllosilicates are unable to impartthe desired Theological properties reliably at all times and under allcircumstances. For instance, it may happen that the originallyformulated viscosity of the aqueous basecoat materials provided withthese phyllosilicates falls sharply on storage or on use at thecustomer's premises, thereby reducing the stability and deleteriouslyaltering the metallic effect, in particular, in the aqueous basecoats inquestion.

[0004] The causes of this phenomenon, which may cause great problems inpractice, are not yet fully understood. It is assumed that thephenomenon is related to the mechanism of rheology buildup in themonomorillonite, by way of dipoles within its molecular structure.Extremely damaging effects are exerted here by ionic materials and bymaterials which have strong electrical fields, examples being trivalentferric ions, which have a particularly small ionic radius. Ferric ionsof this kind are introduced into the aqueous basecoat materials by way,for example, of pigments. Surfactants and molecules with strong dipolesmay also manifest themselves in an adverse manner.

[0005] Other Theological aids, such as thickeners based on polyurethanesor polyacrylates (cf. Römpp Lexikon Lacke und Druckfarben, Georg ThiemeVerlag, Stuttgart, N.Y., “thickeners”, pages 599 to 600), do not havethese disadvantages. On the other hand, however, they have otherdisadvantages which prevent their use in the aqueous basecoat materials.These disadvantages include, in particular, a too weakly pronouncedrheological effect and an absent thixotropic effect, and alsoinsufficient stability, inadequate atomizability, and excessivesensitivity to a reduction in the pH of the aqueous basecoat materialsin question.

[0006] A further disadvantage of the inorganic phyllosilicates is thatthey sometimes have adverse effects on the stability of aluminum effectpigments used in the aqueous basecoat material, with the consequencethat they begin to gas if passivation is inadequate. In general, thiscan be remedied to a certain extent by chromating the surface of thealuminum effect pigments; however, chromating is not entirelyunobjectionable from an environmental standpoint and is increasinglybeing shunned by users.

[0007] Another key disadvantage of the inorganic phyllosilicates is thatthey can be used exclusively in aqueous systems. The addition of sizablefractions of water-miscible organic solvents to aqueous basecoatmaterials prepared using said phyllosilicates causes streaking, phaseseparation, and flocculation. These adverse qualities make itimpossible, for example, to use the customary and known, cost-effectivedilute rinses to clean equipment and containers which have come intocontact with the aqueous basecoat materials in question; instead, it isnecessary to use special rinsing fluids such as mixtures of water,propanol, and butylene glycol.

[0008] A further disadvantage of the known aqueous basecoat material isthat they have to be prepared in a plurality of stages, the sequence inwhich the constituents are incorporated being extremely critical for thesuccess of the process. Moreover, it is frequently impossible to prepareconcentrates having high solids contents, which is a disadvantage forstorage and transportation.

[0009] Problems of rheology and thixotropy also occur, however, inpigment-free aqueous clearcoat materials.

[0010] Clearcoat materials are used to produce clearcoats and arefrequently employed together with aqueous basecoat materials as part ofthe wet-on-wet process for producing multicoat color and/or effectcoating systems on primed and unprimed substrates. In this process, asis known, basecoat films are applied to the substrates and aresubsequently dried but not fully cured. The basecoat films are thenovercoated with clearcoat films, after which both films are fully curedtogether.

[0011] Customary and known aqueous clearcoat materials are one-component(1K), two-component (2K) or multicomponent (3K, 4K) clearcoat materialscurable thermally and/or with actinic radiation.

[0012] Aqueous one-component (1K) clearcoat materials comprise, inparticular, hydroxyl-containing, water-soluble and/or water-dispersiblebinders, and also crosslinking agents such as blocked polyisocyanates,tris(alkoxycarbonylamino)triazine and/or amino resins.

[0013] Aqueous two-component (2K) and multicomponent (3K, 4K) clearcoatmaterials, as described, for example, in the European patent EP-A-0 654052 (international patent application WO 94/03512), comprise—as isknown—water-soluble and/or water-dispersible binders, containingisocyanate-reactive functional groups, especially hydroxyl groups, andalso polyisocyanate crosslinking agents, the two components being storedseparately from one another prior to their use.

[0014] Also known are siloxane clearcoat materials, which may beprepared by reacting hydrolyzable silicon compounds with water or waterdonors and which comprise organic constituents for the purpose ofimproving certain properties. Those materials are sold, for example,under the brand name ORMOCER® (organically modified ceramic). A generaldescription of such systems can be found, for example, in the article byBruce M. Novak, “Hybrid Nanocomposite Materials—Between InorganicGlasses and Organic Polymers”, in Advanced Materials, 1993, 5, No. 6,pp. 422-433, or in the paper by R. Kasemann, H. Schmidt, 15^(th)International Conference, International Centre for Coatings Technology,Paper 7, “Coatings for mechanical and chemical protection based onorganic-inorganic sol-gel nanocomposites”, 1993.

[0015] In order to formulate the specifically desired rheological andthixotropic properties of the aqueous clearcoat materials, a largenumber of Theological aids are employed, examples being thepolyurethane-based associative thickeners known from Römpp, op. cit.,Georg Thieme Verlag, Stuttgart, New York, 1998, “thickeners”, pages 599to 600, and the textbook “Lackadditive” [Additives for coatings] byJohan Bieleman, Wiley-VCH, Weinheim, N.Y., 1998, pages 51 to 59 and 65.The thickeners known to date cannot, however, be used immediately, i.e.,universally, in any aqueous clearcoat material, but instead have to bevery carefully selected and matched to the specific case in hand.

[0016] Rheological aids based on urea urethanes are known and areavailable commercially. They are made up of diamines, diisocyanates, andpolyalkylene glycol monoalkyl ethers as blocking agents for theisocyanate groups, and are commonly employed in solution inwater-miscible solvents. Their use in aqueous compositions, especiallyin aqueous coating materials, adhesives, and sealing compounds curablephysically, thermally, or thermally and with actinic radiation, washitherto impossible.

[0017] It is an object of the present invention to open up new fields ofapplication, especially in aqueous coating materials, adhesives, andsealing compounds, for the known Theological aids based on ureaurethanes, without such use being accompanied by the above-describeddisadvantages of the prior art.

[0018] It is a further object of the present invention to find a novelaqueous composition, curable physically, thermally, or thermally andwith actinic radiation, which no longer has the disadvantages of theprior art but which instead can be prepared in a simple process in asingle step, the sequence of addition of the constituents being oflittle or no significance, which is stable as a concentrate, even with asolids content of more than 40% by weight, on storage and in transit,which has extremely stable pseudoplastic and thixotropic propertieswhich are unaffected even by trivalent ferric ions, strong dipolesand/or strong electrical fields, and which may readily be processed toaqueous and conventional coating materials, adhesives, and sealingcompounds which are curable physically, thermally, or thermally and withactinic radiation.

[0019] Accordingly we have found the novel aqueous composition curablephysically, thermally, or thermally and with actinic radiation,comprising at least one compound containing urea and urethane groups andof the general formula I:

X[NH—C(═O)—NH—Y—NH—C(═O)—OR]₂   (I),

[0020] in which the variables have the following definition:

[0021] R denotes identical or different polyalkylene glycol etherradicals;

[0022] X denotes divalent substituted or unsubstituted arylene radical;

[0023] Y denotes identical divalent, substituted or unsubstitutedarylene radicals identical to or different from the radical X, or

[0024] denotes different divalent, substituted or unsubstituted aryleneradicals, of which none or one is identical to the radical X.

[0025] In the text below, the new novel aqueous composition curablephysically, thermally, and thermally and with actinic radiation isreferred to as the “composition of the invention”.

[0026] Also found has been the novel process for preparing aqueouscoating materials, adhesives, and sealing compounds, which involves

[0027] (1) preparing an aqueous or anhydrous composition curablephysically, thermally, or thermally and with actinic radiation andcomprising at least one compound, containing urea and urethane groups,of the general formula I:

X[NH—C(═O)—NH—Y—NH—C(═O)—OR]₂   (I),

[0028] in which the variables have the following definition:

[0029] R denotes identical or different poly(alkylene-ether) radicals;

[0030] X denotes divalent substituted or unsubstituted arylene radical;

[0031] Y denotes identical divalent, substituted or unsubstitutedarylene radicals identical to or different from the radical X, or

[0032] denotes different divalent, substituted or unsubstituted aryleneradicals, of which none or one is identical to the radical X;

[0033] from its constituents by mixing, and

[0034] (2) diluting the resulting composition with water.

[0035] Also found has been the novel process for preparing aqueouscoating materials, adhesives, and sealing compounds, which involves

[0036] (1) preparing an aqueous composition curable physically,thermally, or thermally and with actinic radiation and comprising atleast one compound, containing urea and urethane groups, of the generalformula I:

X[NH—C(═O)—NH—Y—NH—C(═O)—OR]₂   (I),

[0037] in which the variables have the following definition:

[0038] R denotes identical or different poly(alkylene-ether) radicals;

[0039] X denotes divalent substituted or unsubstituted arylene radical;

[0040] Y denotes identical divalent, substituted or unsubstitutedarylene radicals identical to or different from the radical X, or

[0041] denotes different divalent, substituted or unsubstituted aryleneradicals, of which none or one is identical to the radical X;

[0042] from its constituents by mixing, and

[0043] (2) diluting the resulting composition with at least one organicsolvent or with a mixture of at least one solvent and water.

[0044] In the text below, the novel processes for preparing aqueouscoating materials, adhesives and sealing compounds are referred tocollectively as the “processes of the invention”.

[0045] Additionally found, furthermore, have been the novel coatings,adhesive films, and seals on and in primed and unprimed substrates,which are producable from the compositions of the invention and/or bythe processes of the invention and which are referred to below as the“coatings, adhesive films or seals of the invention”.

[0046] Found not least have been the novel primed and unprimedsubstrates which have at least one coating, adhesive film and/or seal ofthe invention and which are referred to below as “substrates of theinvention”.

[0047] Further subject matter of the invention will emerge from thefollowing description.

[0048] In the light of the prior art it was surprising and unforeseeablefor a skilled worker that the object on which the present invention isbased might be achieved with the aid of the specifically selectedcompounds I for use in accordance with the invention. Indeed, it wasmore likely that only a complicated variation in the binder basis wouldbring forth the effects of the invention. However, it was possible toachieve this objective by the comparatively very much simpler variationof the Theological aid, the resulting compositions of the inventionsurprisingly being of broad applicability and being outstandinglysuitable for the production of aqueous systems. This was especiallysurprising in view of the fact that the compounds I for use inaccordance with the invention had hitherto not been considered for usein aqueous systems.

[0049] The composition of the invention is physically curing. In thecontext of the present invention, the term “physical curing” denotes thecuring of a layer of a coating material by filming as a result of lossof solvent from the coating material, with linking within the coatingtaking place by looping of the polymer molecules of the binders(regarding the term, cf. Römpp, op. cit., “Binders”, pages 73 and 74).Or else filming takes place by way of the coalescence of binderparticles (cf. Römpp, op. cit., “Curing”, pages 274 and 275). Normally,no crosslinking agents are required for this purpose. If desired, thephysical curing may be assisted by atmospheric oxygen or by exposure toactinic radiation.

[0050] The composition of the invention may also be thermally curing(thermosetting). In this case it may be self-crosslinking or externallycrosslinking. In the context of the present invention, the term“self-crosslinking” refers to the property of a binder of undergoingcrosslinking reactions with itself. A prerequisite for this is that thebinders already contain both kinds of complementary reactive functionalgroups which are necessary for crosslinking. Externally crosslinking, onthe other hand, is the term used to refer to those compositions of theinvention wherein one kind of the complementary reactive functionalgroups is present in the binder and the other kind is present in acuring agent or crosslinking agent. For further details of this,reference is made to Römpp, op. cit., “curing”, pages 274 to 276,especially the bottom of page 275.

[0051] Furthermore, the composition of the invention is curablethermally and with actinic radiation, this being referred to by those inthe art as dual cure. In the context of the present invention, actinicradiation means electromagnetic radiation, such as visible light, UVradiation or X-rays, especially UV radiation, and corpuscular radiationsuch as electron beams.

[0052] The composition of the invention is aqueous. This means that itsconstituents are present in solution and/or dispersion in water or in amixture comprising water and minor amounts of at least onewater-miscible organic solvent. Minor amounts here mean amounts which donot destroy the aqueous nature of the mixture.

[0053] The inventively key constituent of the composition of theinvention is the compound I, containing urea groups and urethane groups,of the above-described general formula I.

[0054] In the general formula I, the variable R represents identical ordifferent poly(alkylene ether) radicals. It is of advantage inaccordance with the invention to use identical poly(alkylene ether)radicals R. It is further advantageous to use hydrophilic poly(alkyleneether) radicals R.

[0055] In the context of the present invention, the property of beinghydrophilic means the constitutional property of a molecule or of afunctional group to penetrate the aqueous phase or to remain therein.Accordingly, the property of being hydrophobic in the context of thepresent invention denotes the constitutional property of a molecule orof a functional group to behave exophilically with respect to water,i.e., to tend not to penetrate water, or to depart from the aqueousphase. For further details, reference is made to Römpp op. cit.,“hydrophilicity”, “hydrophobicity”, pages 294 and 295.

[0056] Advantageous hydrophilic poly(alkylene ether) radicals R arethose of the general formula II:

—(—R¹—O—)_(n)—R²   (II),

[0057] in which the index and the variables have the followingdefinition:

[0058] n=2 to 10, preferably 2 to 8, more preferably 2 to 6, and inparticular 3 to 5;

[0059] R¹=alkanediyl radical having 2 to 4 carbon atoms; and

[0060] R²=alkyl radical having 1 to 6 carbon atoms or cycloalkyl radicalhaving 4 to 7 carbon atoms.

[0061] Examples of suitable alkanediyl radicals R¹ are ethane-1,2-diyl,propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl orbutane-1,4-diyl radicals, of which the ethane-1,2-diyl radicals are ofparticular advantage and are therefore used with particular preferencein accordance with the invention.

[0062] Examples of suitable alkyl radicals R² are methyl, ethyl, propyl,butyl, pentyl, hexyl or heptyl radicals, especially butyl radicals.

[0063] Examples of suitable cycloalkyl radicals R² are cyclobutyl,cyclopentyl, cyclohexyl or cyclohexyl radicals.

[0064] In accordance with the invention, the alkyl radicals R² are ofadvantage and are therefore used with preference.

[0065] Examples of especially suitable poly(alkylene ether) radicals Rare triethylene glycol, tetraethylene glycol or pentaethylene glycolmonobutyl ether radicals, of which the triethylene glycol monobutylether radical is especially advantageous and is therefore used with veryparticular preference in accordance with the invention.

[0066] In the general formula I, the variables X and Y representdivalent substituted or unsubstituted arylene radicals.

[0067] In any given compound I for use in accordance with the invention,identical arylene radicals Y may be used. In this case, the aryleneradicals Y may be identical to or different from the arylene radical X.In accordance with the invention it is of advantage if the aryleneradicals Y are different from the arylene radical X.

[0068] Furthermore, in any given compound I for use in accordance withthe invention, use may be made of arylene radicals Y which are differentfrom one another. In this case, one or no arylene radical Y may beidentical to the arylene radical X. In accordance with the invention, itis of advantage here too if no arylene radical Y is identical to thearylene radical X.

[0069] In accordance with the invention it is of advantage if in anygiven compound I for use in accordance with the invention the aryleneradicals Y are identical.

[0070] Examples of suitable arylene radicals X and Y are phen-1,2-,-1,3- or -1,4-ylene radicals, naphth-1,2-, -1,3-, -1,4-, -1,5-, -1,6-,-1,7-, -1,8- or -2,3-ylene radicals, biphenyl-4,4′-, -4,3′-, -4,2′-,-3,3′-or -2,2′-ylene radicals, methanediphenyl-4,4′-, -4,3′-, -4,2′-,-3,3′- or 2,2′-yelene radicals, ethane-1,1-diphenyl-4,4′-, -4,3′-,-4,2′-, -3,3′- or -2,2′-ylene radicals, or propane-2,2-diphenyl-4,4′-,-4,3′-, -4,2′-, -3,3′- or -2,2′-ylene radicals. Of these, the phenyleneradicals are of advantage and are therefore used with preference.

[0071] In accordance with the invention, the substituted aryleneradicals X and Y are of particular advantage and are therefore used withparticular preference.

[0072] Substituents which may be used are all electron withdrawing orelectron donating atoms or organic radicals which do not give rise toany unwanted secondary reactions during the preparation of the compoundsI for use in accordance with the invention and/or during the storage andsubsequent processing of the compositions of the invention and/or duringthe storage and use of the coating materials, adhesives, and sealingcompounds of the invention. The skilled worker will therefore easily beable to identify suitable substituents on the basis of his or hergeneral knowledge in the art.

[0073] Examples of suitable substituents are halogen atoms, especiallychlorine and fluorine, nitrile groups, nitro groups, alkyl, cycloalkyl,alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl,arylalkyl and arylcycloalkyl radicals, and also partly or fullyhalogenated, especially chlorinated and/or fluorinated, alkyl,cycloalkyl, alkycycloalkyl, cycloalkylalkyl, aryl, alkylaryl,cycloalkylaryl, arylalkyl and arylcycloalkyl radicals, especially alkylradicals; aryloxy, alkyloxy and cycloalkyloxy radicals, especiallyphenoxy, naphthoxy, methoxy, ethoxy, propoxy, butyloxy or cyclohexyloxy;arylthio, alkylthio and cycloalkylthio radicals, especially phenylthio,naphthylthio, methylthio, ethylthio, propylthio, butylthio orcyclohexylthio; and tertiary amino groups, especially N,N-dimethylamino,N, N-diethylamino, N, N-dipropylamino, N,N-diphenylamino,N,N-dicyclohexylamino, N-cyclohexyl-N-methylamino, orN-ethyl-N-methylamino. Of these, the alkyl radicals are of particularadvantage and are therefore used with preference. Very particularadvantages result from the use of methyl radicals.

[0074] Examples of particularly preferred arylene radicals X and Y,therefore, are methyl-substituted phenylene radicals which are derivedfrom toluene, o-, m- or p-xylene or their technical-grade mixtures, orfrom sym-trimethylbenzene, pseudocumene or hemellitene or theirtechnical-grade mixtures, such as tol-2,3-, -2,4-, -2,5-, -2,6-, -3,4-or -3,5-ylene radicals, o-xyl-3,4-, -3,5- or -3,6-ylene radicals,m-xyl-2,4- or -2,5-ylene radicals, p-xyl-2,3-, -2,5- or -2,6-yleneradicals, 1,3,4-trimethylphen-1,4-ylene radicals,1,2,4-trimethylphen-3,5-, -3,6- or -5,6-ylene radicals, or1,2,3-trimethylphen-4,5- or -4,6-ylene radicals. Of these, themethyl-substituted phenyl radicals which derive from toluene, especiallythe tol-2,4- and -2,6-ylene radicals, and also the methyl-substitutedphenylene radicals which derive from the technical-grade xylenemixtures, afford very particular advantages and are therefore used withvery particular preference in accordance with the invention. Furtheradvantages result if the arylene radicals X derive from thetechnical-grade xylene mixtures, and the arylene radicals Y fromtoluene.

[0075] Examples of very particularly preferred compounds I for use inaccordance with the invention are the compounds I-1 to I-4, and mixturesthereof.

[0076] In terms of method, the preparation of the compounds I for use inaccordance with the invention has no special features but instead takesplace in accordance with the customary and known methods of organicisocyanate chemistry from suitable starting compounds, with or withoutthe use of customary and

[0077] known catalysts such as dibutyltin oxide or dibutyltin dilaurate,using the customary and known apparatus for reacting polyisocyanates andalso the corresponding precautionary measures.

[0078] Suitable starting compounds X for introducing the above-describedarylene radicals X are the corresponding arylenediamines, especially thexylylenediamines.

[0079] Suitable starting compounds Y for introducing the above-describedarylene radicals X are the corresponding arylene diisocyanates,especially the tolylene diisocyanates.

[0080] Suitable starting compounds R for introducing the above-describedpoly(alkylene ether) radicals are the corresponding poly(alkyleneglycol) monoalkyl ethers or monocycloalkyl ethers, especiallytriethylene glycol monobutyl ether.

[0081] Preferably, the starting compounds X, Y and R are reacted withone another in a molar ratio of (0.8 to 1.2):(1.8 to 2.2):(1.9 to 2.3)and, in particular, 1.0:2.0:2.0.

[0082] The amount of the compounds I for use in accordance with theinvention in the compositions of the invention may vary very widely. Atthe bottom end, the amount is limited by the minimum amount of compoundI for use in accordance with the invention which still just brings aboutthe desired technical effects. At the top end it is limited by theviscosity developed in the composition of the invention. Accordingly,the amount will generally be chosen such that the composition of theinvention does not become too viscous to be handled. The amountpreferably, based in each case on the composition, is from 0.1 to 10,more preferably from 0.2 to 8, with particular preference from 0.3 to 6,with very particular preference from 0.4 to 4, and in particular from0.5 to 3% by weight.

[0083] The compound I for use in accordance with the invention may beemployed in one hundred percent form. In accordance with the inventionit is of advantage to use it in solutions in at least one organicsolvent, especially a water-miscible organic solvent such asN-methylpyrrolidone. It is preferred in this case to employ solidscontents of from 10 to 80 and, in particular, from 30 to 70% by weight.

[0084] The composition of the invention further comprises constituentsas customary and known for coating materials, adhesives, and sealingcompounds which are curable physically, thermally, or thermally and withactinic radiation.

[0085] A further constituent which is particularly important forperformance is at least one binder which essentially renders thecompositions of the invention curable physically, thermally, orthermally and with actinic radiation.

[0086] Examples of suitable binders are random, alternating and/orblock, linear and/or branched and/or comb, addition (co)polymers ofethylenically unsaturated monomers, or polyaddition resins and/orpolycondensation resins. For further details of these terms, referenceis made to Römpp, op. cit., page 457, “polyaddition” and “polyadditionresins (polyadducts)”, and also pages 463 and 464, “polycondensates”,“polycondensation”, and “polycondensation resins”.

[0087] Examples of suitable binders of the kind mentioned above forcompositions of the invention that are curable physically or thermally,especially thermally, are poly(meth)acrylates or acrylate copolymers,especially those described in the patent DE-A-197 36 535 or DE-A-197 41554; polyesters, especially those described in the patent DE-A-40 09 858or DE-A-44 37 535; alkyds, acrylated polyesters, polylactones,polycarbonates, polyethers, epoxy resin-amine adducts,(meth)acrylatediols, partially saponified polyvinyl esters, polyureas orpoly-urethanes, of which the polyurethanes, the acrylate copolymersand/or the polyesters are particularly advantageous and thepolyurethanes are very particularly advantageous.

[0088] These binders contain reactive functional groups which arecontained with complementary reactive functional groups in the bindersthemselves (self-crosslinking) or in crosslinking agents (externalcrosslinking).

[0089] Examples of suitable complementary reactive functional groups foruse in accordance with the invention which enter into crosslinkingreactions are summarized in the overview below. In the overview, thevariable R³ represents an acyclic or cyclic aliphatic, an aromatic,and/or an aromatic-aliphatic (araliphatic) radical; the variables R⁴ andR⁵ represent identical or different aliphatic radicals or are linkedwith one another to form an aliphatic or heteroaliphatic ring. Overview:Examples of complementary functional groups in the binder andcrosslinking agent or crosslinking agent and binder —SH —C(O)—OH —NH₂—C(O)—O—C(O)— —OH —NCO —O—(CO)—NH—(CO)—NH₂ —NH—C(O)—OR³ —O—(CO)—NH₂—CH₂OH —CH₂—O—CH₃ —NH—C(O)—CH(—C(O)OR³)₂ —NH—C(O)—CH(—C(O)OR³)(—C(O)—R³)—NH—C(O)—NR⁴R⁵ ═Si(OR³)₂

—C(O)—OH

—O—C(O)—CR³═CH2 —OH —O—CR³═CH₂ —NH₂ —C(O)—CH₂—C(O)—R³ —CH═CH₂

[0090] The selection of the respective complementary groups is guided onthe one hand by the consideration that they should not enter into anyunwanted reactions in the course of storage and/or, in the case of dualcure, should not disrupt or inhibit the curing with actinic radiation,and secondly by the temperature range within which the thermal curing isto take place.

[0091] It is of advantage in this case, in accordance with the inventionand especially in respect of thermally sensitive substrates such asplastics, to choose a temperature range which does not exceed 100° C.,especially 80° C. In the light of these boundary conditions, hydroxylgroups and isocyanate groups, or carboxyl groups and epoxy groups, haveproven advantageous as complementary functional groups, and so areemployed with preference in accordance with the invention in the coatingmaterials, adhesives, and sealing compounds of the invention which arepresent in the form of two-component or multicomponent systems.Particular advantages result here if the hydroxyl groups are used asreactive functional groups and the isocyanate groups as complementaryreactive functional groups.

[0092] Where higher crosslinking temperatures may be employed, forexample, from 100° C. to 180° C., suitable coating materials, adhesives,and sealing compounds of the invention include one-component systems aswell, in which the reactive functional groups are preferably thio,amino, hydroxyl, carbamate, allophanate, carboxyl, and/or (meth)acrylategroups, but especially hydroxyl groups, and the complementary reactivefunctional groups are preferably anhydride, carboxyl, epoxy, blockedisocyanate, urethane, methylol, methylol ether, siloxane, amino,hydroxyl and/or beta-hydroxyalkylamide groups, but especially blockedisocyanate, urethane, methylol or methylol ether groups.

[0093] Where the compositions of the invention are to be curable notonly thermally but also with actinic radiation (dual cure), they furthercomprise customary and known binders which can be activated with actinicradiation. Examples of suitable binders which can be activated withactinic radiation are (meth)acryloyl-, allyl-, vinyl- ordicyclopentadienyl-functional (meth)acrylate copolymers or polyetheracrylates, polyester acrylates, unsaturated polyester acrylates, epoxyacrylates, urethane acrylates, amino acrylates, melamine acrylates,silicone acrylates, or the corresponding methacrylates. It is, however,also possible to employ binders which contain functional groups whichcan be activated with actinic radiation and reactive functional groupswhich are able to undergo thermal crosslinking reactions.

[0094] Examples of the polyurethanes used with very particularpreference are ionically and/or nonionically stabilized polyurethaneswhich are saturated, unsaturated, and/or grafted with olefinicallyunsaturated compounds.

[0095] Advantageously, depending on the nature of the stabilization, thepolyurethanes have an acid number or amine number of from 10 to 250 mgKOH/g (ionic stabilization or nonionic plus ionic stabilization) or offrom 0 to 10 mg KOH/g (nonionic stabilization), an OH number of from 30to 350 mg KOH/g, and a number average molecular weight of from 1500 to55,000 daltons.

[0096] The method of preparing the polyurethanes is arbitrary. They arepreferably obtainable by preparing, in a first process step, apolyurethane prepolymer which contains at least one free isocyanategroup.

[0097] The polyurethane prepolymer is of linear, branched or comb, butespecially linear, construction. In this context the linear polyurethaneprepolymer includes preferably two free isocyanate groups, especiallytwo terminal free isocyanate groups. The branched or comb-constructedpolyurethane prepolymers include preferably at least two, in particularmore than two, free isocyanate groups, terminal free isocyanate groupsbeing preferred.

[0098] In terms of method, the preparation of the polyurethaneprepolymers for use in accordance with the invention has no specialfeatures but instead takes place, for example, as described in patentEP-A-0 089 497, DE-C-197 22 862 , DE-A-196 45 761, EP-A-0 522 419 orEP-A-0 522 420, by reaction of a polyol, especially a diol, with atleast one polyisocyanate, especially a diisocyanate, the isocyanatecomponent being employed in a molar excess so as to give terminal freeisocyanate groups.

[0099] For the preparation of the polyurethane prepolymers it ispreferred to use diisocyanates and also, if desired, in minor amounts,polyisocyanates, for the purpose of introducing branches. In the contextof the present invention, minor amounts are amounts which do not causegelling of the polyurethane prepolymers during their preparation. Thismay also be prevented by using small amounts of monoisocyanates.

[0100] Examples of suitable diisocyanates are iso-phorone diisocyanate(i.e., 5-isocyanato-1-isocyan ato-methyl-1,3,3-trimethylcyclohexane),5-isocyanato-1-(2-isocyanatoeth-1-yl)-1,3,3-trimethylcyclohexane,5-iso-cyanato-1-(3-isocyanatoprop-1-yl)-1,3,3-trimethylcyclo-hexane,5-isocyanato-(4-isocyanatobut-1-yl)-1,3,3-tri-methylcyclohexane,1-isocyanato-2-(3-isocyanatoprop-1-yl)cyclohexane,1-isocyanato-2-(3-isocyanatoeth-1-yl)-cyclohexane,1-isocyanato-2-(4-isocyanatobut-1-yl)-cyclohexane,1,2-diisocyanatocyclobutane, 1,3-diiso-cyanatocyclobutane,1,2-diisocyanatocyclopentane, 1,3-diisocyanatocyclopentane,1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane,1,4-diisocyanatocyclo-hexane, dicyclohexylmethane 2,4′-diisocyanate,tri-methylene diisocyanate, tetramethylene diisocyanate, pentamethylenediisocyanate, hexamethylene diiso-cyanate, ethylethylene diisocyanate,trimethylhexane diisocyanate, heptane methylene diisocyanate ordiisocyanates derived from dimeric fatty acids, as marketed under thecommercial designation DDI 1410 by the company Henkel and described inthe patents DO 97/49745 and WO 97/49747, especially2-heptyl-3,4-bis(9-isocyanatononyl)-1-pentylcyclohexane, or 1,2-, 1,4-or 1,3-bis(isocyanatomethyl)cyclohexane, 1,2-, 1,4- or1,3-bis(2-isocyanatoeth-1-yl)cyclohexane,1,3-bis(3-isocyanatoprop-1-yl)cyclohexane, 1,2-, 1,4- or1,3-bis(4-isocyanatobut-1-yl)cyclohexane, liquidbis(4-isocyanatocyclohexyl)methane with a trans/trans content of up to30% by weight, preferably 25% by weight, and in particular 20% byweight, as is described by the patents DE-A-44 14 032, GB-A-1220717,DE-A-16 18 795 or DE-A-17 93 785; tetramethylxylylidene diisocyanate(TMXDI® from CYTEC), tolylene diisocyanate, xylylene diisocyanate,bisphenylene diisocyanate, naphthylene diisocyanate or diphenylmethanediisocyanate.

[0101] Examples of suitable polyisocyanates based on the diisocyanatesdescribed above are isocyanato-containing polyurethane prepolymers,which have been prepared by reacting polyols with an excess of at leastone of the above-described diisocyanates, and/or polyisocyanatescontaining isocyanurate, biuret, allo-phanate, iminooxadiazinedione,urethane, urea and/or uretdione groups. It is preferred to usepolyiso-cyanates containing on average from 2.5 to 5 isocyanate groupsper molecule and having viscosities of from 100 to 10,000, preferablyfrom 100 to 5000 mPas. Furthermore, the polyisocyanates may have beensubjected to conventional hydrophilic or hydrophobic modification.

[0102] Very particular preference is given to mixtures ofpolyisocyanates which contain uretdione and/or isocyanurate and/orallophanate groups and which are based on the above-describeddiisocyanates as formed by catalytic oligomerization of diisocyanatesusing appropriate catalysts.

[0103] Examples of suitable monoisocyanates are phenyl isocyanate,cyclohexyl isocyanate or stearyl iso-cyanate, or vinyl isocyanate,methacryloylisocyanate, and/or1-(l-isocyanato-1-methylethyl)-3-(1-methyl-ethenyl)benzene (TMI® fromCYTEC).

[0104] Examples of suitable polyols are saturated or olefinicallyunsaturated polyesterpolyols which are prepared by reacting

[0105] unsulfonated or sulfonated saturated and/or unsaturatedpolycarboxylic acids or their esterifiable derivatives, alone ortogether with monocarboxylic acids, and

[0106] saturated and/or unsaturated polyols, alone or together withmonools.

[0107] Examples of suitable polycarboxylic acids are aromatic, aliphaticand cycloaliphatic polycarboxylic acids. Preference is given to the useof aromatic and/or aliphatic polycarboxylic acids.

[0108] Examples of suitable aromatic polycarboxylic acids are phthalicacid, isophthalic acid, terephthalic acid, phthalic, isophthalic orterephthalic acid monosulfonate, or halophthalic acids, such astetrachlorophthalic or tetrabromophthalic acid, among which isophthalicacid is advantageous and is therefore used with preference.

[0109] Examples of suitable acyclic aliphatic or unsaturatedpolycarboxylic acids are oxalic acid, malonic acid, succinic acid,glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,sebacic acid, undecanedicarboxylic acid or dodecanedicarboxylic acid, ordimeric fatty acids or maleic acid, fumaric acid or itaconic acid, ofwhich adipic acid, glutaric acid, azelaic acid, sebacic acid, dimericfatty acids and maleic acid are advantageous and are therefore used withpreference.

[0110] Examples of suitable cycloaliphatic and cyclic unsaturatedpolycarboxylic acids are 1,2-cyclo butanedicarboxylic acid,1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid,1,3-cyclo-pentanedicarboxylic acid, hexahydrophthalic acid,1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexane-dicarboxylic acid,4-methylhexahydrophthalic acid, tricyclodecanedicarboxylic acid,tetrahydrophthalic acid or 4-methyltetrahydrophthalic acid. Thesedicarboxylic acids may be used both in their cis and in their trans formand also as a mixture of both forms.

[0111] Also suitable are the esterifiable derivatives of theabovementioned polycarboxylic acids, such as their monoesters orpolyesters with aliphatic alcohols having 1 to 4 carbon atoms or hydroxyalcohols having 1 to 4 carbon atoms, for example. It is also possible touse the anhydrides of the abovementioned polycarboxylic acids, wherethey exist.

[0112] Together with the polycarboxylic acids it is also possible ifdesired to use monocarboxylic acids, such as, for example, benzoic acid,tert-butylbenzoic acid, lauric acid, isononanoic acid, fatty acids ofnaturally occurring oils, acrylic acid, methacrylic acid, ethacrylicacid or crotonic acid. The preferred monocarboxylic acid used isisononanoic acid.

[0113] Examples of suitable polyols are diols and triols, especiallydiols. Normally, triols are used alongside the diols in minor amounts inorder to introduce branches into the polyester polyols.

[0114] Suitable diols are ethylene glycol, 1,2- or 1,3-propanediol,1,2-, 1,3- or 1,4-butanediol, 1,2-, 1,3-, 1,4- or 1,5-pentanediol, 1,2-,1,3-, 1,4-, 1,5-or 1,6-hexanediol, neopentyl hydroxypivalate, neopentylglycol, diethylene glycol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,2-, 1,3-or 1,4-cyclohexane-dimethanol, trimethylpentanediol,ethylbutylpropane-diol, the positionally isomeric diethyloctanediols2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-methyl-1,3-propanediol,2-phenyl-2-methyl-1,3-propanediol, 2-propyl-2-ethyl-1,3-propanediol,2-di-tert-butyl-1,3-propanediol, 2-butyl-2-propyl-1,3-propanediol,1-di-hydroxymethylbicyclo[2.2.1]heptane, 2,2-diethyl-1,3-propanediol,2,2-dipropyl-1,3-propanediol 2-cyclohexyl-2-methyl-1,3-propanediol,2,5-dimethyl-2,5-hexanediol, 2,5-diethyl-2,5-hexanediol,2-ethyl-5-methyl-2,5-hexanediol, 2,4-dimethyl-2,4-pentanediol,2,3-dimethyl-2,3-butanediol, 1,4-bis(2′-hydroxypropyl)benzene and1,3-bis(2′-hydroxypropyl)benzene. These diols may also be used per sefor the preparation of the polyurethanes.

[0115] Of these diols, hexanediol and neopentyl glycol are particularlyadvantageous and are therefore used with particular preference.

[0116] Examples of suitable triols are trimethylol-ethane,trimethylolpropane or glycerol, especially trimethylolpropane.

[0117] The abovementioned triols may also be used per se to prepare thepolyurethanes (A) for inventive use (cf. the patent EP-A-0 339 433).

[0118] If desired, minor amounts of monools may also be used. Examplesof suitable monools are alcohols or phenols such as ethanol, propanol,n-butanol, sec-butanol, tert-butanol, amyl alcohols, hexanols, fattyalcohols, allyl alcohol, or phenol.

[0119] The polyesterpolyols may be prepared in the presence of smallamounts of a suitable solvent as entrainer. Examples of entrainers usedare aromatic hydrocarbons, such as especially xylene and(cyclo)aliphatic hydrocarbons, e.g., cyclohexane or methylcyclohexane.

[0120] Further examples of suitable polyols are polyesterdiols which areobtained by reacting a lactone with a diol. They are notable for thepresence of terminal hydroxyl groups and repeating polyester fractionsof the formula —(—CO—(CHR ⁶)_(m)—CH₂—O—)—. Here, the index m ispreferably from 4 to 6 and the substituent R⁶ is hydrogen or an alkyl,cycloalkyl, or alkoxy radical. No substituent contains more than 12carbon atoms. The total number of carbon atoms in the substituent doesnot exceed 12 per lactone ring. Examples are hydroxycaproic acid,hydroxybutyric acid, hydroxydecanoic acid, and/or hydroxystearic acid.

[0121] Preferred for the preparation of the polyesterdiols is theunsubstituted ###-caprolactone, where m is 4 and all substituents R⁶ arehydrogen. The reaction with lactone is started by low molecular masspolyols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, ordimethylolcyclohexane. It is also possible, however, to react otherreaction components, such as ethylenediamine, alkyldialkanolamines, orelse urea, with caprolactone. Other suitable diols of relatively highmolecular mass are polylactamdiols, which are prepared by reacting, forexample, ###-caprolactam with low molecular mass diols.

[0122] Further examples of suitable polyols include polyetherpolyols,especially those having a number-average molecular weight of from 400 to5000, in particular from 400 to 3000. Examples of highly suitablepolyetherdiols are polyetherdiols of the general formulaH—(—O—(CHR⁷)_(o)—)_(p)OH, where the substituent R⁷ is hydrogen or alower, unsubstituted or substituted alkyl radical, the index o is from 2to 6, preferably from 3 to 4, and the index p is from 2 to 100,preferably from 5 to 50. Especially suitable examples are linear orbranched polyetherdiols such as poly(oxyethylene) glycols,poly(oxypropylene) glycols, and poly(oxybutylene) glycols.

[0123] The polyetherdiols should, firstly, not introduce excessiveamounts of ether groups, since otherwise the polyurethanes formed startto swell in water. Secondly, they may be used in amounts which ensurethe nonionic stabilization of the polyurethanes. In that case they actas the functional nonionic groups described below.

[0124] The polyurethane comprises alternatively

[0125] functional groups convertible into cations by neutralizing agentsand/or quaternizing agents, and/or cationic groups, especially ammoniumgroups,

[0126] or

[0127] functional groups convertible into anions by neutralizing agents,and/or anionic groups, especially carboxylic acid and/or carboxylategroups,

[0128] and/or

[0129] nonionic hydrophilic groups, especially poly(alkylene ether)groups.

[0130] Examples of suitable functional groups which are convertible intocations by neutralizing agents and/or quaternizing agents are primary,secondary or tertiary amino groups, secondary sulfide groups or tertiaryphosphine groups, especially tertiary amino groups or secondary sulfidegroups.

[0131] Examples of suitable cationic groups are primary, secondary,tertiary or quaternary ammonium groups, tertiary sulfonium groups orquaternary phosphonium groups, preferably quaternary ammonium groups ortertiary sulfonium groups, but especially tertiary sulfonium groups.

[0132] Examples of suitable functional groups which are convertible intoanions by neutralizing agents are carboxylic acid, sulfonic acid orphosphonic acid groups, especially carboxylic acid groups.

[0133] Examples of suitable anionic groups are carboxylate, sulfonate orphosphonate groups, especially carboxylate groups.

[0134] Examples of suitable neutralizing agents for functional groupsconvertible into cations are organic and inorganic acids such as formicacid, acetic acid, lactic acid, dimethylolpropionic acid, citric acid,sulfuric acid, hydrochloric acid, and phosphoric acid.

[0135] Examples of suitable neutralizing agents for functional groupsconvertible into anions are ammonia, ammonium salts, such as ammoniumcarbonate or ammonium bicarbonate for example, and also amines, such astrimethylamine, triethylamine, tributylamine, dimethyl-aniline,diethylaniline, triphenylamine, dimethyl-ethanolamine,diethylethanolamine, methyldiethanol-amine, triethanolamine and thelike, for example. Neutralization may take place in organic phase or inaqueous phase. A preferred neutralizing agent used isdimethylethanolamine.

[0136] The amount of neutralizing agent used overall in the compositionsof the invention is chosen so that from 1 to 100 equivalents, preferablyfrom 50 to 90 equivalents, of the potentially cationic or anionicfunctional groups of the polyurethane are neutralized.

[0137] Of these functional (potentially) ionic groups and functionalnonionic groups, the (potentially) anionic groups are advantageous andare therefore used with particular preference.

[0138] The introduction of (potentially) anionic groups into thepolyurethane molecules takes place by way of the incorporation ofcompounds which contain in the molecule at least one isocyanate-reactivegroup and at least one group capable of forming anions; the amount to beused may be calculated from the target acid number.

[0139] Examples of suitable compounds of this kind are those containingtwo isocyanate-reactive groups in the molecule. In particular, suitableisocyanate-reactive groups are hydroxyl groups, and primary and/orsecondary amino groups. Accordingly it is possible, for example, to usealkanoic acids having two substituents on the ### carbon atom. Thesubstituent may be a hydroxyl group, an alkyl group, or, preferably, analkylol group. These alkanoic acids have at least one, generally from 1to 3, carboxyl groups in the molecule. They have 2 to about 25,preferably 3 to 10, carbon atoms. Examples of suitable alkanoic acidsare dihydroxypropionic acid, dihydroxysuccinic acid, anddihydroxybenzoic acid. A particularly preferred group of alkanoic acidsare the ###,###-dimethylolalkanoic acids of the general formulaR⁸—C(CH₂OH)₂COOH, R⁸ being a hydrogen atom or an alkyl group having upto about 20 carbon atoms. Examples of especially suitable alkanoic acidsare 2,2-dimethylolacetic acid, 2,2-dimethylol-propionic acid,2,2-dimethylolbutyric acid, and 2,2-dimethylolpentanoic acid. Thepreferred dihydroxy-alkanoic acid is 2,2-dimethylolpropionic acid.Examples of compounds containing amino groups are ###,###-diaminovalericacid, 3,4-diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid, and2,4-diaminodiphenyl ether sulfonic acid. If desired, monohydroxy- and/ormonomercaptocarboxylic acids such as hydroxyacetic acid or thioglycolicacid may also be used.

[0140] Nonionic stabilizing poly(oxyalkylene) and/or poly(alkyleneether) groups may be introduced as lateral or terminal groups into thepolyurethane molecules. For this purpose it is possible to use, forexample, alkoxypoly(oxyalkylene) alcohols and/or poly(alkylene glycol)monoalkyl ethers having the general formula R⁹O—(—CH₂—CHR¹⁰—O—)_(r)H,where R⁹ is an alkyl radical having 1 to 6 carbon atoms, R¹⁰ is ahydrogen atom or an alkyl radical having 1 to 6 carbon atoms, and theindex r is a number between 20 and 75 (cf. the patents EP-A-0 354 261 orEP-A-0 424 705).

[0141] The use of polyols, polyamines and amino alcohols brings about anincrease in the molecular weight of the polyurethanes.

[0142] Suitable polyols for the chain extension are polyols having up to20 carbon atoms per molecule, such as ethylene glycol, diethyleneglycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol,1,4-butane-diol, 1,2-butylene glycol, 1,6-hexanediol,trimethylol-propane, castor oil or hydrogenated castor oil,ditrimethylolpropane ether, pentaerythritol, 1,2-cyclohexanediol,1,4-cyclohexanedimethanol, bisphenol A, bisphenol F, neopentyl glycol,neopentyl glycol hydroxypivalate, hydroxyethylated or hydroxypropylatedbisphenol A, hydrogenated bisphenol A, or mixtures thereof (cf. patentsEP-A-0 339 433, EP-A-0 436 941, EP-A-0 517 707).

[0143] Examples of suitable polyamines have at least two primary and/orsecondary amino groups. Polyamines are essentially alkylene polyamineshaving 1 to 40 carbon atoms, preferably about 2 to 15 carbon atoms. Theymay carry substituents which have no hydrogen atoms that are reactivewith isocyanate groups. Examples are polyamines having a linear orbranched aliphatic, cycloaliphatic or aromatic structure and at leasttwo primary amino groups.

[0144] Diamines include hydrazine, ethylenediamine, propylenediamine,1,4-butylenediamine, piperazine, 1,4-cyclohexyldimethylamine,1,6-hexamethylenediamine, trimethylhexamethylenediamine,menthanediamine, iso-phoronediamine, 4,4′-diaminodicyclohexylmethane,and aminoethyleneothanolamine. Preferred diamines are hydrazine, alkyl-or cycloalkyldiamines such as propylenediamine and1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane.

[0145] It is also possible to use polyamines containing more than twoamino groups in the molecule. In these cases, however, it should beensured—for example, by using monoamines as well—that no crosslinkedpolyurethane resins are obtained. Polyamines of this kind which may beused are diethylenetriamine, triethylenetetramine, dipropylene-diamine,and dibutylenetriamine. An example of a monoamine is ethylhexylamine(cf. the patent EP-A-0 089 497).

[0146] Examples of suitable amino alcohols are ethanolamine anddiethanolamine.

[0147] The polyurethanes may contain lateral and/or terminalolefinically unsaturated groups. Groups of this kind may be introduced,for example, with the aid of compounds containing at least oneisocyanate-reactive group, especially hydroxyl group, and at least onevinyl group. Examples of suitable compounds of this kind aretrimethylolpropane monoallyl ether and trimethylolpropanemono(meth)acrylate.

[0148] The polyurethanes may be grafted with ethylenically unsaturatedcompounds. Examples of suitable polyurethanes in the form of graftcopolymers are known from the patents EP-A-0 521 928, EP-A-0 522 420,EP-A-0 522 419 or EP-A-0 730 613.

[0149] The proportion of the binders, especially of the polyurethanes,in the compositions of the invention may vary extremely widely and isguided primarily by the intended use of the compositions and, ifappropriate, by the functionality of the binders with respect to thecrosslinking reaction with the crosslinking agents, where present. Inaccordance with the invention it is of advantage to use the binders inan amount, based in each case on the composition, of from 2.0 to 90,preferably from 3.0 to 85, with particular preference from 4.0 to 80,with very particular preference from 5.0 to 75, and in particular from6.0 to 70% by weight. As regards the polyurethanes, it is of particularadvantage in accordance with the invention to use the amounts asdescribed in the patents EP-A-0 089 497, DE-C-197 22 862, DE-A-196 45761, EP-A-0 522 419 and EP-A-0 522 420.

[0150] A further key performance constituent of the compositions of theinvention is at least one color and/or effect pigment.

[0151] The pigments may comprise organic and inorganic compounds. On thebasis of this large number of appropriate pigments, therefore, thecoating material especially the aqueous basecoat and solid color topcoatmaterial, particularly the aqueous basecoat material of the inventionensures a universal breadth of application and permits the realizationof a large number of color shades and optical effects.

[0152] Effect pigments which may be used include metal flake pigmentssuch as commercial aluminum bronzes, aluminum bronzes chromated inaccordance with DE-A-36 36 183, and commercial stainless steel bronzes,and also nonmetallic effect pigments, such as pearlescent pigments andinterference pigments, for example. For further details, reference ismade to Römpp, op. cit., page 176, “effect pigments” and pages 380 and381 “metal oxide-mica pigments” to “metal pigments”.

[0153] Examples of suitable inorganic color pigments are titaniumdioxide, iron oxides, sicotrans yellow, and carbon black. Examples ofsuitable organic color pigments are thioindigo pigments, indanthreneblue, Cromophthal red, Irgazine orange and Heliogen green. For furtherdetails, reference is made to Römpp, op. cit., pages 180 and 181, “ironblue pigments” to “black iron oxide”, pages 451 to 453 “pigments” to“pigment volume concentration”, page 563 “thioindigo pigments”, and page567 “titanium dioxide pigments”.

[0154] The pigments are preferably incorporated in paste form into thecompositions of the invention, in which case suitable grinding resinsinclude the binders described above.

[0155] The pigment content of the coating material of the invention mayvary extremely widely and is guided primarily by the hiding power of thepigments, the desired shade, and the desired optical effect. In thecomposition of the invention, the pigments are present in an amount ofpreferably from 0.5 to 50, more preferably from 0.5 to 45, withparticular preference from 0.5 to 40, with very particular preferencefrom 0.5 to 35, and in particular from 0.5 to 30% by weight, based ineach case on the overall weight of the composition. The pigment/binderratio as well, i.e., the ratio of the pigments to the binders, may varyextremely widely. This ratio is preferably from 6.0:1.0 to 1.0:50, morepreferably from 5:1.0 to 1.0:50, with particular preference from 4.5:1.0to 1.0:40, with very particular preference from 4:1.0 to 1.0:30, and inparticular from 3.5:1.0 to 1.0:25.

[0156] The use of these pigments is omitted when the compositions of theinvention are used to prepare the clearcoat materials of the inventionor the pigment-free adhesives and sealing compounds of the invention.

[0157] Yet another key performance constituent of the compositions ofthe invention is at least one crosslinking agent for the thermalcrosslinking or curing. Its use is omitted when the compositions of theinvention are physically curing or self-crosslinking, or when they areused to prepare the corresponding coating materials, adhesives, andsealing compounds of the invention.

[0158] Suitable crosslinking agents preferably contain the complementarygroups described above. Examples of suitable crosslinking agents are.amino resins such as melamine resins or urea resins, resins or compoundscontaining anhydride groups, resins or compounds containing epoxidegroups, tris(alkoxycarbonylamino)-triazines, resins or compoundscontaining carbonate groups, blocked and/or unblocked polyisocyanates,beta-hydroxyalkylamides, and compounds containing on average at leasttwo groups capable of transesterification, examples being reactionproducts of malonic diesters and polyisocyanates or of esters andpartial esters of polyhydric alcohols of malonic acid withmonoiso-cyanates, as described in the European patent EP-A-0 596 460.Crosslinking agents of this kind are well known to the skilled workerand are offered as commercial products by numerous companies.

[0159] Depending on the reactivity of the further crosslinking agent, itmay be added directly to the compositions of the invention, producingwhat is known as a one-component system. If, however, it is aparticularly reactive crosslinking agent, such as a polyisocyanate or anepoxide, it is generally not added to the coating materials of theinvention until shortly before use. The result in this case is what isknown as a two-component or multicomponent system.

[0160] The crosslinking agent content of the compositions of theinvention may vary extremely widely and is guided primarily by thefunctionality of the above-described binders. The crosslinking agentsare used in an amount, based in each case on the composition, ofpreferably from 0.5 to 50, more preferably from 1.0 to 45, withparticular preference from 1.5 to 40, with very particular preferencefrom 2.0 to 35, and, in particular, from 2.5 to 30% by weight.

[0161] Still another key performance constituent of the compositions ofthe invention is at least one reactive diluent for the thermal curing orfor the curing with actinic radiation.

[0162] Examples of suitable reactive diluents for thermal curing areoligomeric polyols obtainable by hydroformylation and subsequenthydrogenation from oligomeric intermediates themselves obtained bymetathesis reactions of acyclic monoolefins and cyclic monoolefins;examples of suitable cyclic monoolefins are cyclobutene, cyclopentene,cyclohexene, cyclo-octene, cycloheptene, norbornene and 7-oxanorbornene;examples of suitable acyclic monoolefins are contained in hydrocarbonmixtures which are obtained in petroleum processing by cracking (C₅cut); examples of suitable oligomeric polyols for use in accordance withthe invention have a hydroxyl number of from 200 to 450, a numberaverage molecular weight Mn of from 400 to 1000, and a mass averagemolecular weight Mw of from 600 to 1100; further examples of suitablepolyols are branched, cyclic and/or acyclic C₉-C₁₆ alkanesfunctionalized with at least two hydroxyl groups, especiallydiethyloctanediols.

[0163] Further examples of polyols for use are hyperbranched compoundshaving a tetrafunctional central group, derived fromditrimethylolpropane, diglycerol, ditrimethylolethane, pentaerythritol,tetrakis(2-hydroxyethyl)methane, tetrakis(3-hydroxy-propyl)methane or2,2-bishydroxymethyl-1,4-butanediol (homopentaerythritol). Thesereactive diluents may be prepared by the customary and known methods ofpreparing hyperbranched and dendrimeric compounds. Suitable synthesismethods are described, for example, in the patent WO 93/17060 or WO96/12754, or in the book by G. R. Newkome, C. N. Moorefield and F.Vögtle, “Dendritic Molecules, Concepts, Syntheses, Perspectives”, VCH,Weinheim, N.Y., 1996.

[0164] Suitable radiation-curable reactive diluents includepolyfunctional, ethylenically unsaturated compounds of low molecularmass. Examples of suitable such compounds are esters of acrylic acidswith polyols, such as neopentyl glycol diacrylate, trimethylolpropanetriacrylate, pentaerythritol triacrylate or pentaerythritoltetraarylate; or reaction products of hydroxyalkyl acrylates withpolyisocyanates, especially aliphatic polyisocyanates. For furtherdetails, reference is made to Römpp, op. cit., “reactive diluents”, page491.

[0165] The composition of the invention may further comprise effectiveamounts of additives as commonly used in coating materials, adhesivesand sealing compounds. Examples of suitable additives are:

[0166] organic and inorganic fillers such as chalk, calcium sulfate,barium sulfate, silicates such as talc or kaolin, silicas, oxides suchas aluminum hydroxide or magnesium hydroxide, nanoparticles, or organicfillers such as textile fibers, cellulose fibers, polyethylene fibers orwood flour;

[0167] UV absorbers;

[0168] free-radical scavengers;

[0169] crosslinking catalysts;

[0170] slip additives;

[0171] polymerization inhibitors;

[0172] defoamers;

[0173] emulsifiers, especially nonionic emulsifiers such as alkoxylatedalkanols, polyols, phenols and alkylphenols or anionic emulsifiers suchas alkali metal salts or ammonium salts of alkanecarboxylic acids,alkanesulfonic acids and sulfo acids of alkoxylated alkanols, polyols,phenols and alkylphenols;

[0174] wetting agents such as siloxanes, fluorine compounds, carboxylicmonoesters, phosphates, polyacrylic acids and their copolymers, orpolyurethanes;

[0175] adhesion promoters;

[0176] leveling agents;

[0177] film-forming auxiliaries such as cellulose derivatives;

[0178] flame retardants;

[0179] waxes, examples being acrylic copolymer waxes dissolved inorganic solvents;

[0180] rheology control additives, such as those known from the patentsWO 94/22968, EP-A-0 276 501 EP-A-0 249 201, WO 97/12945; crosslinkedpolymeric microparticles, as disclosed for example in EP-A-0 008 127;inorganic phyllosilicates, such as aluminum-magnesium silicates,sodium-magnesium and sodium-magnesium-fluorine-lithium phyllosilicatesof the montmorillonite type; silicas such as Aerosils; or syntheticpolymers containing ionic and/or associative groups, such as polyvinylalcohol, poly(meth)acrylamide, poly(meth)acrylic acid,polyvinylpyrrolidone, styrene-maleic anhydride or ethylene-maleicanhydride copolymers and their derivatives or hydrophobically modifiedethoxylated urethanes or polyacrylates; or

[0181] photoinitiators, such as photoinitiators of the Norrish II type,whose mechanism of action is based on an intramolecular variant of thehydrogen abstraction reactions as occur diversely in the case ofphotochemical reactions; by way of example, reference may be made hereto Römpp Chemie Lexikon, 9^(th), expanded and revised edition, GeorgThieme Verlag, Stuttgart, Vol. 4, 1991, or Römpp Lexikon Lacke undDruckfarben, Georg Thieme Verlag, Stuttgart, N.Y. 1998,“photo-initiators”, pages 444 to 446.

[0182] Further examples of suitable coatings additives are described inthe textbook “Lackadditive” [Additives for coatings] by Johan Bieleman,Wiley-VCH, Weinheim, N.Y., 1998.

[0183] Viewed in terms of its method, the preparation of the compositionof the invention has no special features but instead takes place by themixing of its constituents, in which context it is possible to employprimary or secondary dispersion methods and also customary and knownmixing equipment such as stirred vessels, dissolvers, stirred mills, orextruders.

[0184] The compositions of the invention serve preferably to prepare thecoating materials, adhesives, and sealing compounds of the invention,but especially the coating materials of the invention. In thisapplication, the compositions of the invention exhibit very particularadvantages. Thus they may be prepared at high concentration and can bestored without problems as concentrates, already including all of theconstituents needed for their subsequent end use. They need only beadjusted with water and/or with at least one water-miscible organicsolvent to the viscosity required for the respective application—andonly in an amount just sufficient for the end use in question.Accordingly, the compositions of the invention are outstandinglysuitable, in particular, for preparing very small amounts, as have to beprovided, for example, for special colors in automotive OEM finishingor, generally, for automotive refinish. Here, the use of thecompositions of the invention proves to be particularly advantageousboth technically and economically.

[0185] In accordance with the invention it is of advantage to start fromcompositions of the invention curable physically, thermally, orthermally and with actinic radiation which contain water or aresubstantially free from water, and which are then diluted with water. Inthe context of the present invention, “substantially free from water”refers to a water content composed solely of the amounts introduced byway of the individual hydrous constituents.

[0186] In accordance with the invention it is also of advantage to startfrom compositions of the invention curable physically, thermally, orthermally and with actinic radiation which contain water, and which arethen diluted with at least one organic solvent or a mixture of at leastone solvent and water, to give conventional coating materials, adhesivesand sealing compounds.

[0187] The resultant adhesives of the invention are used to produce theadhesive films of the invention on the primed and unprimed substratesdescribed below.

[0188] The resultant sealing compounds of the invention are used toproduce the seals of the invention on and in the primed and unprimedsubstrates described below.

[0189] The resultant coating materials of the invention are used toproduce the coatings of the invention on the primed and unprimedsubstrates described below.

[0190] In this technological field, the compositions of the inventionhave very particular advantages and may be employed very widely. Forinstance, depending on their composition, the coating materials of theinvention may be used as surfacers to produce surfacer coats orantistonechip primer coats, as basecoat materials, especially aqueousbasecoat materials, to produce basecoats, as solid-color topcoatmaterials to produce solid-color topcoats, or as clearcoat materials toproduce clearcoats. With particular preference, the coating materials ofthe invention are employed for the preparation of basecoat materials,especially aqueous basecoat materials, or solid-color topcoat materials.

[0191] The basecoat material of the invention, especially the aqueousbasecoat material of the invention, is outstandingly suitable for theproduction of multicoat color and/or effect coating systems on primedand unprimed substrates by the wet-on-wet technique. Moreover, thesolid-color topcoat material of the invention is outstandingly suitablefor the production of single-coat color and/or effect coatings.

[0192] The coating material of the invention exhibits particularadvantages in its use as an aqueous basecoat material as part of thewet-on-wet technique, wherein the aqueous basecoat material is appliedto the primed or unprimed substrate and dried, but not cured, aclearcoat material is subsequently applied to the aqueous basecoat film,and the resulting clearcoat film is cured together with the aqueousbasecoat film, thermally or thermally and with actinic radiation (dualcure).

[0193] Suitable substrates are all surfaces for coating which are notdamaged by curing of the films present thereon using heat, or heat andactinic radiation in combination (dual cure); for example, metals,plastics, wood, ceramic, stone, textile, fiber assemblies, leather,glass, glass fibers, glass wool and rock wool, mineral-bound andresin-bound building materials, such as plasterboard and cement slabs orroof tiles, and composites of these materials. Accordingly, themulticoat systems of the invention are also suitable for applicationsoutside those of automotive OEM finishing and automotive refinish aswell. In this context they are particularly suitable for the coating offurniture and for industrial coating, including coil coating andcontainer coating. In the context of industrial applications they aresuitable for coating virtually all parts for private or industrial use,such as radiators, domestic appliances, small metal parts such as nutsand bolts, hub caps, wheel rims, or packaging.

[0194] In the case of electrically conductive substrates it is possibleto use primers, which are prepared in a customary and known manner fromelectrodeposition coating materials. Both anodic and cathodicelectrodeposition coating materials are suitable for this purpose, butespecially cathodics. Normally, especially in the painting ofautomobiles, a surfacer coat or antistonechip primer coat, which may beregarded as part of the primer, is applied over the electrocoat.

[0195] It is also possible to coat, bond or seal parts of primed orunprimed plastics, for example, ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF,MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PC, PC/PBT, PC/PA, PET,PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC,PP-EPDM and UP (abbreviations to DIN 7728T1). In the case ofunfunctionalized and/or nonpolar substrate surfaces, these may besubjected prior to coating in a known manner to a pretreatment, such aswith a plasma or by flaming, or may be provided with a water-basedprimer.

[0196] The aqueous basecoat materials of the invention may be applied byany standard method, such as spraying, knifecoating, brushing,flowcoating, dipping, impregnating, trickling or rolling, for example.The substrate to be coated may itself be at rest, with the applicationdevice or unit being moved. Alternatively, the substrate to be coated,especially a coil, may be moved, with the application unit being at restrelative to the substrate or being moved appropriately. Where theaqueous basecoat materials of the invention include constituents whichcan be activated with actinic radiation, application is conductedpreferably in the absence of light. These application methods may ofcourse also be used for the application of the clearcoat film as part ofthe wet-on-wet technique of the invention.

[0197] Possibly following a certain rest period, which is used for thefilms to flow out and/or for the volatile constituents to evaporate, theaqueous basecoat films and clearcoat films applied may be cured in acustomary and known manner, thermally or thermally and with actinicradiation.

[0198] In terms of its method, the thermal curing has no specialfeatures; instead, the customary and known temperatures in the rangefrom room temperature to 200° C., curing times in the range from oneminute to three hours, and equipment such as radiant heaters orforced-air ovens are used.

[0199] The curing with actinic radiation also has no special features interms of its method, but instead takes place in a customary and knownmanner by irradiation with UV lamps and/or electron beam sources,preferably under inert gas.

[0200] In the case of conjoint curing of the dual-cure aqueous basecoatfilms of the invention with the clearcoat films, thermal curing andactinic radiation curing may be employed simultaneously or inalternation. Where the two curing methods are used in alternation, it ispossible, for example, to commence with thermal curing and to end withactinic radiation curing. In other cases it may prove advantageous tocommence and to end with actinic radiation curing. The skilled worker isable to determine the curing method most advantageous for the case inhand on the basis of his or her general knowledge in the art, with orwithout the assistance of simple preliminary tests.

[0201] In this context it is found to be a further particular advantageof the aqueous basecoat material of the invention that, in the contextof the wet-on-wet technique, all customary and known clearcoatmaterials, as well as the clearcoat materials of the invention, may becombined with the aqueous basecoat film of the invention.

[0202] Examples of suitable known one-component (1K), two-component (2K)or multicomponent (3K, 4K) clearcoat materials are known from thepatents DE-A-42 04 518, U.S. Pat. No. 5,474,811, U.S. Pat. No.5,356,669, U.S. Pat. No. 5,605,965, WO 94/10211, WO 94/10212, WO94/10213, EP-A-0 594 068, EP-A-0 594 071, EP-A-0 594 142, EP-A-0 604992, WO 94/22969, EP-A-0 596 460 and WO 92/22615.

[0203] One-component (1K) clearcoat materials comprise, as is known,hydroxyl-containing binders and crosslinking agents such as blockedpolyisocyanates, tris(alkoxycarbonylamino)triazines and/or amino resins.In a further variant they comprise polymers containing lateral carbamateand/or allophanate groups as binders and amino resins modified withcarbamate and/or with allophanate as crosslinking agents (cf. U.S. Pat.No. 5,474,811, U.S. Pat. No. 5,356,669, U.S. Pat. No. 5,605,965, WO94/10211, WO 94/10212, WO 94/10213, EP-A-0 594 068, EP-A-0 594 071 orEP-A-0 594 142).

[0204] Two-component (2K) or multicomponent (3K, 4K) clearcoat materialscomprise as their key constituents, as is known, hydroxyl-containingbinders and polyisocyanate crosslinking agents, which are storedseparately until they are used.

[0205] Examples of suitable powder clearcoat materials are known, forexample, from the German patent DE-A-42 22 194 or from the BASFLacke+Farben AG product information bulletin “Pulverlacke” [powdercoating materials], 1990.

[0206] The key constituents of powder clearcoat materials are, as isknown, binders containing epoxide groups, and polycarboxylic acids ascrosslinking agents.

[0207] Examples of suitable powder slurry clearcoat materials are known,for example, from the U.S. Pat. No. 4,268,542 and from the German patentapplications DE-A-195 18 392.4 and DE-A-196 13 547, or are described inthe German patent application DE-A-198 14 471.7, unpublished at thepriority date of the patent specification.

[0208] Powder slurry clearcoat materials, as is known, comprise powderclearcoat materials dispersed in an aqueous medium.

[0209] UV-curable clearcoat materials are disclosed, for example, in thepatents EP-A-0 540 884, EP-A-0 568 967, and U.S. Pat. No. 4,675,234.

[0210] Within the multicoat system of the invention, the thickness ofthe individual coats may vary widely. In accordance with the invention,however, it is of advantage for the aqueous basecoat film to have athickness of from 5 to 25 μm, in particular from 7 to 20 μm, and for theclearcoat film to have a thickness of from 15 to 120 μm, preferably from40 to 80 μm, and in particular from 60 to 70 μm.

[0211] The single-coat and multicoat systems of the invention haveoutstanding optical, mechanical, and chemical properties. For instance,they are free from any surface defects such as shrinkage (wrinkling).Moreover, they possess particularly high hiding power, outstandingintercoat adhesion, and outstanding optical effects, especially metalliceffects.

[0212] Overall, the primed and unprimed substrates coated with a coatingof the invention, bonded with an adhesive film of the invention, and/orsealed with a sealing compound of the invention have a particularlyoutstanding properties profile, especially particularly long servicelife, which makes them particularly attractive, both technically andeconomically, to the user.

EXAMPLES Examples 1 to 4

[0213] The Preparation of Thermally Curable Inventive Compositions andCoating Materials

[0214] For Examples 1 to 4, the following constituents were provided orprepared:

[0215] 1. Polyurethane Dispersion A:

[0216] The polyurethane dispersion A was prepared in accordance with theinstructions specified in the German patent DE-A-44 37 535 on page 7lines 21 to 34, “B preparation of an aqueous polyurethane dispersion”,from 248.82 parts by weight of a polyester diol, prepared from 1.81 molof a dimeric fatty acid (Pripol® 1009 from Unichema; dimer content atleast 98% by weight, trimer content not more than 2% by weight, monomercontent not more than traces), 0.82 mol of isophthalic acid, 0.61 mol ofhexanediol, and 0.61 mol of neopentyl glycol, 2.64 parts by weight ofneopentyl glycol, 15.27 parts by weight of dimethylolpropionic acid,77.07 parts by weight of m-tetramethylxylylene diisocyanate, 13.16 partsby weight of trimethylol-propane, and 8.41 parts by weight ofdimethylethanol-amine, and was adjusted to a solids content of 31% byweight.

[0217] 2. Secondary Aqueous Acrylic Dispersion A:

[0218] The secondary aqueous acrylic dispersion A was prepared exactlyas described in the German patent DE-A-44 37 535 on page 8 lines 25 to49, “E preparation of an aqueous polyacrylate dispersion”. The solidscontent of the dispersion was 40% by weight.

[0219] 3. Aqueous Solution of a Polyester A:

[0220] The aqueous solution of a polyester A was prepared in analogy tothe instructions specified in the German patent DE-A-44 37 535 on page 7lines 6 to 19, “preparation of an aqueous polyester resin solution”,from 97.8 parts by weight of neopentyl glycol, 62 parts by weight ofhexahydrophthalic anhydride, 229 parts by weight of dimeric fatty acidPripol® 1009, 111 parts by weight of hexanediol, 102.9 parts by weightof trimellitic anhydride, and 2.3 parts by weight ofdimethylethanolamine, using 20 parts by weight of xylene, (entrainer)and 20 parts by weight of butyl Cellosolve (cosolvent), and was adjustedwith water to a solids content of 60% by weight.

[0221] 4. Aqueous Solution of a Polyester B:

[0222] The aqueous solution of a polyester A was prepared in accordancewith the instructions specified in the German patent DE-A-44 37 535 onpage 7 lines 6 to 19, “preparation of an aqueous polyester resinsolution”. Instead of the 158 parts by weight of dimethylethanolaminespecified therein, however, 16.2 parts by weight of dimethylethanolaminewere used.

[0223] 5. Flatting Paste (White-Gray):

[0224] The flatting paste was prepared by mixing 30 parts by weight ofthe polyester solution B from section 4, 46 parts by weight of butylglycol, 12 parts by weight of a 10% strength solution ofdimethyl-ethanolamine in water, and 12 parts by weight of a commercialpyrogenic silica (Syloid® ED 3).

[0225] 6. Aqueous Tinting Paste (White):

[0226] The aqueous tinting paste was prepared by mixing 63.7 parts byweight of the above-described polyurethane dispersion A (cf. section 1),2.7 parts by weight of deionized water, 32 parts by weight of acommercial titanium dioxide pigment of the rutile type (Titan® UV L530), 0.3 parts by weight of a commercial pyrogenic silica (Aerosil® R972) and 1.3 parts by weight of a 10% strength solution ofdimethylethanol-amine in water.

[0227] 7. Aqueous Tinting Paste (Colorless, Transparent):

[0228] The aqueous tinting paste was prepared by mixing 62.9 parts byweight of the above-described polyurethane dispersion A (cf. section 1),2.0 parts by weight of a commercial polyetherpolyol (Pluriol® P 900) 0.9parts by weight of Aerosil® R972, 30 parts by weight of a commercialtitanium dioxide pigment of the rutile type (Titan Rutil Tayca® MT500HD), 3.8 parts by weight of deionized water and 0.4 part by weight of a10% strength solution of dimethylethanolamine in water.

[0229] 8. Metallic Pigment:

[0230] 65% suspension of aluminum flakes (Alu-Stapa Hydrolux® 2192 fromEckart).

[0231] 9. Crosslinking Agent:

[0232] 9.1 Commercial melamine resin solution (72% strength) (Cymel®203)

[0233] 9.2 Commercial melamine resin (99.9% strength) (Cymel® 1133)

[0234] 10. Wetting Agent:

[0235] Commercial wetting agent (Byk® 345 from Byk Chemie).

[0236] 11. Compound I for Inventive Use (Urea Urethane):

[0237] Commercial Theological additive (Byk® 410 from Byk Chemie; 52%strength in N-methylpyrrolidone).

[0238] 12. Polyurethane Dispersion B:

[0239] The polyurethane dispersion B was prepared in accordance with theinstructions specified in the German patent DE 43 39 870 Al in column11, line 47 to column 12 line 20, “1. Preparation of an inventive binderdispersion”.

[0240] 13. Wax Paste:

[0241] 6% dispersion of an acrylic copolymer wax in butylacetate/xylene.

Examples 1 to 3

[0242] The Preparation of an Inventive Composition and the Preparationof an Inventive Aqueous Basecoat Material (Example 1) and ofConventional Basecoat Materials (Examples 2 and 3) Therefrom

[0243] The composition of the invention was prepared by mixing thefollowing constituents, described above, in the stated amounts:

[0244] 21.0 parts by weight of constituent 1,

[0245] 5.0 parts by weight of constituent 2,

[0246] 4.0 parts by weight of constituent 3,

[0247] 1.6 parts by weight of constituent 5,

[0248] 3.9 parts by weight of constituent 6,

[0249] 0.9 part by weight of constituent 7,

[0250] 5.0 parts by weight of constituent 8,

[0251] 4.5 parts by weight of constituent 9.1,

[0252] 0.1 part by weight of constituent 10,

[0253] 5.0 parts by weight of constituent 11,

[0254] 5.0 parts by weight of isopropanol, and

[0255] 6.0 parts by weight of butyl glycol.

[0256] The resulting inventive composition was completely stable onstorage. In particular, there was no change in its viscosity.

[0257] For Example 1, the inventive composition was diluted with 38parts by weight of deionized water, with stirring. This gave an aqueousbasecoat material (solids content: 20.87% by weight) of satin silvercolor, which was likewise entirely stable on storage and which togetherwith a very wide variety of clearcoat materials gave outstandingmulticoat color and/or effect coating systems.

[0258] For Example 2, the inventive composition was diluted with 38parts by weight of isopropanol. This gave a conventional basecoatmaterial (solids content: 20.87% by weight) of satin silver color, whichwas likewise entirely stable on storage and which together with a verywide variety of clearcoat materials gave outstanding multicoat colorand/or effect coating systems.

[0259] For Example 3, the conventional basecoat material of Example 2was diluted further with 32.5 parts by weight of butyl acetate and 7.5parts by weight of butyl diglycol acetate. This gave a diluteconventional basecoat material (solids content: 14.91% by weight) ofsatin silver color, which was likewise entirely stable on storage andwhich together with a very wide variety of clearcoat materials gaveoutstanding multicoat color and/or effect coating systems.

Example 4

[0260] The Preparation of an Inventive Composition and of a DiluteConventional Inventive Basecoat Material Therefrom

[0261] The composition of the invention was prepared by mixing thefollowing constituents, described above, in the stated amounts:

[0262] 21.33 parts by weight of constituent 12,

[0263] 1.07 parts by weight of constituent 5,

[0264] 2.6 parts by weight of constituent 6,

[0265] 0.6 part by weight of constituent 7,

[0266] 4.0 parts by weight of constituent 9.2

[0267] 3.33 parts by weight of constituent 11,

[0268] 3.33 parts by weight of constituent 8,

[0269] 0.04 parts by weight of constituent 10,

[0270] 7.29 parts by weight of constituent 13,

[0271] 26.4 parts by weight of isopropanol, and

[0272] 4.0 parts by weight of butyl glycol.

[0273] The resulting inventive composition which in terms of its naturewas conventional, i.e., containing predominantly organic solvents, wascompletely stable on storage. In particular, there was no change in itsviscosity.

[0274] The inventive composition was diluted with 8.67 parts by weightof solvent naphtha, 8.67 parts by weight of butyl acetate, and 8.67parts by weight of butyl glycol with stirring. This gave a diluteconventional basecoat material (solids content: 17.81% by weight) ofsatin silver color, which was likewise entirely stable on storage andwhich together with a very wide variety of clearcoat materials gaveoutstanding multicoat color and effect coating systems.

[0275] Aqueous Compositions Curable Physically, Thermally, or Thermallyand with Actinic Radiation, Products Thereof, and their Preparation

1. An aqueous composition curable physically, thermally, and/or withactinic radiation, comprising at least one compound containing urea andurethane groups and of the general formula I:X[NH—C(═O)—NH—Y—NH—C(═O)—OR]₂   (I), in which the variables have thefollowing definition: R denotes identical or different poly(alkyleneether) radicals; X denotes divalent substituted or unsubstituted aryleneradical; Y denotes identical divalent, substituted or unsubstitutedarylene radicals identical to or different from the radical X, ordenotes different divalent, substituted or unsubstituted aryleneradicals, of which none or one is identical to the radical X.
 2. Thecomposition as claimed in claim 1, comprising the compound I in anamount, based on the composition, of from 0.1 to 10% by weight.
 3. Thecomposition as claimed in claim 1 or 2, wherein the polyalkylene glycolether radicals R have the general formula II: —(—R¹—O—)_(n)—R²   (II),in which the index and the variables have the following definition: n=2to 10; R¹=alkanediyl radical having 2 to 4 carbon atoms; and R²=alkylradical having 1 to 6 carbon atoms or cycloalkyl radical having 4 to 7carbon atoms.
 4. The composition as claimed in any of claims 1 to 3,wherein substituted and/or unsubstituted phenylene, naphthylene,biphenylylene and/or alkane-diphenylylene radicals are used as radicalsX and Y.
 5. The composition as claimed in claim 4, whereinalkyl-substituted phenylene radicals are used as radicals X and Y.
 6. Aprocess for preparing an aqueous coating material, adhesive, or sealingcompound, which comprises (1) preparing an aqueous or anhydrouscomposition curable physically, thermally, or thermally and with actinicradiation and comprising at least one compound, containing urea andurethane groups, of the general formula I: X[NH—C(═O)—NH—Y—NH—C(═O)—OR]₂  (I), in which the variables have the following definition: R denotesidentical or different poly(alkylene-ether) radicals; X denotes divalentsubstituted or unsubstituted arylene radical; Y denotes identicaldivalent, substituted or unsubstituted arylene radicals identical to ordifferent from the radical X, or denotes different divalent, substitutedor unsubstituted arylene radicals, of which none or one is identical tothe radical X; from its constituents by mixing, and (2) diluting theresulting composition with water.
 7. A process for preparing an aqueouscoating material, adhesive or sealing compound, which comprises (1)preparing an aqueous composition curable physically, thermally, orthermally and with actinic radiation and comprising at least onecompound, containing urea and urethane groups, of the general formula I:X[NH—C(═O)—NH—Y—NH—C(═O)—OR]₂   (I), in which the variables have thefollowing definition: R denotes identical or differentpoly(alkylene-ether) radicals; X denotes divalent substituted orunsubstituted arylene radical; Y denotes identical divalent, substitutedor unsubstituted arylene radicals identical to or different from theradical X, or denotes different divalent, substituted or unsubstitutedarylene radicals, of which none or one is identical to the radical X;from its constituents by mixing, and (2) diluting the resultingcomposition with at least one organic solvent or with a mixture of atleast one solvent and water.
 8. The process as claimed in claim 6 or 7,wherein the compound I is present in the composition (1) in an amount,based on the composition, of from 0.1 to 10% by weight.
 9. The processas claimed in any of claims 6 to 8, wherein the polyalkylene glycolether radicals R have the general formula II: —(—R¹—O—)_(n)—R²   (II),in which the index and the variables have the following definition: n=2to 10; R¹=alkanediyl radical having 2 to 4 carbon atoms; and R²=alkylradical having 1 to 6 carbon atoms or cycloalkyl radical having 4 to 7carbon atoms.
 10. The process as claimed in any of claims 6 to 9,wherein substituted and/or unsubstituted phenylene, naphthylene,biphenylylene and/or alkanediphenylylene radicals are used as radicals Xand Y.
 11. The process as claimed in claim 10, wherein alkyl-substitutedphenylene radicals are used as radicals X and Y.
 12. An aqueous coatingmaterial, adhesive, or sealing compound, preparable from the compositionas claimed in any of claims 1 to 5 and/or by the process as claimed inany of claims 6 to
 11. 13. A coating, adhesive film, or seal on and/orin a primed or unprimed substrate, producable from an aqueous coatingmaterial, adhesive, or sealing compound as claimed in claim
 12. 14. Aprimed or unprimed substrate having at least one coating, adhesive film,and/or seal as claimed in claim 13.